EP1816231A1 - Film de fluorocarbone et procédé servant à produire celui-ci - Google Patents

Film de fluorocarbone et procédé servant à produire celui-ci Download PDF

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Publication number
EP1816231A1
EP1816231A1 EP05800431A EP05800431A EP1816231A1 EP 1816231 A1 EP1816231 A1 EP 1816231A1 EP 05800431 A EP05800431 A EP 05800431A EP 05800431 A EP05800431 A EP 05800431A EP 1816231 A1 EP1816231 A1 EP 1816231A1
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Prior art keywords
substrate surface
film
fluorocarbon film
fluorocarbon
plasma
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EP05800431A
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German (de)
English (en)
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EP1816231A4 (fr
Inventor
Chikaya c/o Asahi Glass Company Ltd. TAMITSUJI
Seiji c/o Asahi Glass Company Limited HIGASHI
Shin c/o Asahi Glass Company Limited TATEMATSU
Satoshi c/o Asahi Glass Company Limited OKI
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AGC Inc
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Asahi Glass Co Ltd
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Publication of EP1816231A1 publication Critical patent/EP1816231A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a process for producing a fluorocarbon film at least a part of which is chemically bonded to a substrate surface, a fluorocarbon film produced by such a process, and a fluorocarbon film provided with a substrate.
  • a fluorocarbon such as polytetrafluoroethylene (PTFE) is excellent in the water and oil repellency, anti-fouling property, release property, weather resistance, low refractive index characteristic, low friction property, chemical resistance, etc., and it is used for various applications.
  • PTFE polytetrafluoroethylene
  • Non-Patent Document 1 a direct fluorination method by means of a fluorine gas
  • Patent Document 2 a plasma polymerization method
  • LB Langmuir-Blodgett
  • Patent Document 2 a vacuum vapor deposition method
  • sputtering method a surface treatment with a fluorinated silane coupling agent, or a fluoropolymer-coating
  • the direct fluorination method by means of a fluorine gas or the plasma polymerization method is, for example, preferred, since a thin film can be formed and at least a part of the fluorocarbon film can be chemically bonded to the substrate surface.
  • the plasma polymerization method wherein a high energy state of plasma is utilized, whereby a monomer (such as a non-vinyl monomer) which is usually difficult to polymerize, may be introduced, and the degree of freedom in designing the film is high, such being desirable.
  • a fluorocarbon is grafted to a substrate surface, and theoretically, it should be possible to obtain a film which has high durability and which is excellent in a functionality such as water and oil repellency.
  • control of the film forming conditions is difficult, and it used to be difficult to constantly form a fluorocarbon film with high durability and high functionality.
  • low energy plasma irradiation is not preferred, since the polymerization rate tends to be thereby substantially slow, and it tends to be difficult to chemically bond the fluorocarbon to the substrate surface.
  • a polytetrafluoroethylene (PTFE) film (not one formed on a substrate) wherein CF 2 groups are linearly chained, and CF groups are little, is obtained.
  • PTFE polytetrafluoroethylene
  • the amount of CF 3 groups is substantially small (e.g. Fig. 3C of Patent Document 4).
  • the amount of CF 2 carbene formed in the plasma polymerization process is controlled by the pulse irradiation of plasma.
  • Patent Document 4 discloses, in Claim 1, "A structure having a fluorocarbon polymer thin film Vietnamese thereon, the polymer film having a fractional composition given as x% CF 2 , (100-x) / 2% CF 3 , (100-x) /2% CF, and substantially 0% C, where x is greater than about 80 and less than 100".
  • Fig. 3B EXAMPLE 1 in the same document, a fluorocarbon film is disclosed which has a composition comprising 65% of CF 2 groups, about 15% of CF 3 groups, and about 10% of CF groups (except for CF 2 groups, the values were read-out from the Fig. by the present inventors).
  • CF groups are increased at the same time as CF 3 groups, and such is entirely different from the technique of the present invention to increase CF 3 groups while decreasing CF groups.
  • the present invention has been made under the above circumstances, and it is an object of the present invention to provide a process for producing a fluorocarbon film, whereby a fluorocarbon film excellent in the durability and functionality (such as water and oil repellency) can be constantly formed by a relatively simple process, and the film may be made thin.
  • Another object is to provide a thin film-form fluorocarbon film excellent in the durability and functionality (such as water and oil repellency), and a fluorocarbon film provided with a substrate having such excellent properties.
  • the present inventors have conducted an extensive study to solve the above problems and have invented the following process for producing a fluorocarbon film.
  • the present invention provides a process for producing a fluorocarbon film, characterized by conducting, in sequence, step (a) for applying plasma to a substrate surface in a continuous or pulse manner to form active points on the substrate surface and step (b) for applying plasma to the substrate surface in a continuous or pulse manner in the presence of a gas of a fluorocompound represented by the formula C x F y and/or C x F y O z (wherein each of x, y and z is a positive integer not including 0) under such a condition that active species impinge on the substrate surface at a relatively lower collision energy than in step (a).
  • plasma irradiation in a continuous manner includes not only continuous irradiation at the same output but also a case where continuous irradiation is carried out when changing the output, such as increasing or decreasing the output.
  • step (b) as a means to carry out plasma irradiation under such a condition that active species impinge on the substrate surface at a relatively lower collision energy than in step (a), it is preferred to change at least one condition, as between steps (a) and (b), among the average plasma output per unit time, the atmosphere pressure and the interelectrode distance.
  • plasma output corresponds to an electric power (discharge power) per unit area applied to the electrodes.
  • average plasma output per unit time is defined, in the case of pulse irradiation, by a value obtained by dividing the output during irradiation by the time for one cycle of irradiation once/non-irradiation once. Accordingly, even with the same absolute output, if the continuous irradiation is switched to pulse irradiation, the output per unit time will decrease.
  • the output per unit time will be 4 W/cm 2 .
  • electrode distance means a distance between the lower electrode and the upper electrode opposingly disposed thereto (plasma discharge is carried out between these electrodes).
  • Step (a) is preferably carried out in the presence of at least one type of gas selected from the group consisting of hydrogen, helium, nitrogen, oxygen, fluorine, argon, carbon monoxide, carbon dioxide, nitrogen dioxide, steam and a gas of a fluorocompound represented by the formula C x F y and/or C x F y O z (wherein each of x, y and z is a positive integer not including 0). It is particularly preferred to use the same gas in steps (a) and (b).
  • at least one type of gas selected from the group consisting of hydrogen, helium, nitrogen, oxygen, fluorine, argon, carbon monoxide, carbon dioxide, nitrogen dioxide, steam and a gas of a fluorocompound represented by the formula C x F y and/or C x F y O z (wherein each of x, y and z is a positive integer not including 0). It is particularly preferred to use the same gas in steps (a) and (b).
  • the fluorocarbon film of the present invention is characterized in that it is produced by the process for producing a fluorocarbon film according to the above-described present invention.
  • the present invention provides a fluorocarbon film at least a part of which is chemically bonded to a substrate surface and which contains at most 8 mol% of CF groups, from 20 to 90 mol% of CF 2 groups and from 10 to 80 mol% of CF 3 groups, based on the total amount of CF groups, CF 2 groups and CF 3 groups.
  • mol% of CF groups, CF 2 groups and CF 3 groups is obtained by taking narrow spectra of the 1s orbit of carbon atoms of a fluorocarbon film by a X-ray photoelectron spectroscopic apparatus (ESCA, Model 5500, manufactured by PHI) and subjecting them to peak division into C, CF, CF 2 and CF 3 .
  • ESA X-ray photoelectron spectroscopic apparatus
  • the fluorocarbon film provided with a substrate of the present invention is characterized in that it comprises the above-mentioned fluorocarbon film formed on the substrate surface.
  • a fluorocarbon film excellent in the durability and functionality (such as water and oil repellency) can be constantly formed by a relatively simple process, and the film may be made thin.
  • the present invention it is possible to provide a thin film-form fluorocarbon film excellent in the durability and functionality (such as water and oil repellency), and a fluorocarbon film provided with a substrate having such excellent properties.
  • the process for producing a fluorocarbon film of the present invention is a process for producing a fluorocarbon film at least a part of which is chemically bonded to a substrate surface, which comprises, in sequence, step (a) for applying plasma to a substrate surface in a continuous or pulse manner to form active points on the substrate surface and step (b) for applying plasma to the substrate surface in a continuous or pulse manner in the presence of a gas of a fluorocompound represented by the formula C x F y and/or C x F y O z (wherein each of x, y and z is a positive integer not including 0) under such a condition that active species impinge on the substrate surface at a relatively lower collision energy than in step (a).
  • step (a) plasma irradiation is carried out under a relatively severe condition to form active points (radicals) to be starting points for film growth, on the substrate surface, and then, in step (b), plasma irradiation is carried out under a relatively mild condition in the presence of a gas of a fluorocompound as a monomer, to let the film grow.
  • the substrate is not particularly limited so long as the active points can be formed by plasma irradiation.
  • the material for the substrate may, for example, be a polyolefin such as polyethylene or polypropylene; a non-fluorinated organic polymer such a polyvinyl chloride, polycarbonate, polyester, polyether, polyamide, polyimide, polyvinyl alcohol, polyurethane or polycellulose; a metal such as copper, iron, stainless steel, aluminum, nickel or an alloy thereof; a metal oxide such as silicon dioxide (such as glass) or aluminum oxide; or a composite material thereof. Particularly preferred is a non-fluorinated organic polymer. Among them, a polyester is more preferred.
  • the substrate may be in any form such as a sheet form, a film form, a flat plate form, a hollow filament form, a cylindrical form, a container form, a rod form, a spherical form, a block form or a powder form.
  • a sheet form, a film form or a flat plate form is preferred.
  • step (a) is a step for forming active points (radicals) which will be starting points for film growth on the substrate surface.
  • the film growth proceeds mainly in step (b).
  • step (a) it is simply required that a sufficient amount of active points are formed on the substrate surface.
  • the gas to be used in step (a) may be any optional gas so long as it is capable of forming active species in the plasma. Namely, in step (a), it is not essential to employ a gas of a fluorocompound as the monomer.
  • step (b) it is essential to employ a gas of a fluorocompound represented by the formula C x F y and/or C x F y O z (wherein each of x, y and z is a positive integer not including 0).
  • a gas of a non-fluorinated compound such as hydrogen, helium, nitrogen, oxygen, fluorine, argon, carbon monoxide, carbon dioxide, nitrogen dioxide or steam may be employed. Otherwise, it is preferred to carry out the step in the presence of a gas of a fluorocompound such as a gas represented by the formula C x F y and/or C x F y O z (wherein each of x, y and z is a positive integer not including 0).
  • a gas of a fluorocompound such as a gas represented by the formula C x F y and/or C x F y O z (wherein each of x, y and z is a positive integer not including 0).
  • the gas one type or a mixture of two or more types may be employed.
  • the gas to be used in step (a) is preferably a gas of a non-fluorinated compound from the viewpoint of production cost, and it is preferably the same gas as in step (b) when the production efficiency or the convenience of the apparatus are taken into consideration.
  • the gas to be used in step (b) is not particularly limited so long as it is a gas of a fluorocompound represented by the formula C x Fy and/or C x FyO z (wherein each of x, y and z is a positive integer not including 0).
  • the gas to be used in step (b) is preferably one having a low global warming coefficient and being capable of readily forming CF 2 carbene required for the film growth.
  • Such a gas of a fluorocompound may, for example, be tetrafluoroethylene, hexafluoropropylene, hexafluoropropylene oxide (HFPO), perfluorobenzene or a compound represented by the following formulae. These gases may be used alone or in combination as a mixture of two or more of them. Further, such a gas may be used for the reaction as diluted with a gas of a non-fluorinated compound.
  • PPVE ... CF 2 CF-O-CF 2 -CF 2 -CF 3
  • PMVE ... CF 2 CF-O-CF 3
  • step (a) plasma irradiation is carried out under such a condition that a sufficient amount of active points can be formed on the substrate surface.
  • step (b) plasma irradiation is carried out under such a condition that active species impinge on the substrate surface at a collision energy relatively lower than in step (a). In each step, the plasma is applied in a continuous or pulse manner.
  • the present inventors have found that it is possible to change the collision energy of the active species on the substrate surface by changing one or more of conditions such as the average plasma output per unit time, the atmosphere pressure and the interelectrode distance. Specifically, it is possible to lower the collision energy of the active species on the substrate surface relatively by e.g. lowering the average plasma output per unit time, by increasing the atmosphere pressure or increasing the interelectrode distance.
  • the average plasma output per unit time is higher, the density in number of active species to be formed in the plasma increases, whereby the collision energy on the substrate surface becomes large. Further, the present inventors have found that in order to change the collision energy of active species on the substrate surface, "the average plasma output per unit time" is more effective than "the peak output of the plasma". Accordingly, even with the same peak output, if the continuous irradiation is switched to pulse irradiation, the average output per unit time will decrease, whereby the collision energy of active species on the substrate surface can be lowered.
  • the change of the condition such as the average output per unit time, the atmosphere pressure or the interelectrode distance after completion of step (a) may be carried out instantaneously, or the condition may be continuously or stepwisely increased or lowered.
  • step (b) For example, in a case where continuous irradiation is carried out in steps (a) and (b), and the plasma output is substantially changed, in order to generate glow plasma constantly, it is preferred to lower the plasma output continuously or stepwisely. In such a case, "the average plasma output per unit time" relatively decreases during this transfer process, which is therefore contained in step (b).
  • the plasma generator is not particularly limited so long as it is capable of generating glow plasma, and a DC discharge type or an AC discharge type may be employed.
  • a DC discharge type or an AC discharge type may be employed as the discharge power source.
  • the discharge power source it is preferred to employ a high frequency power source of 13.56 MHz which is industrially commonly used, from the viewpoint of the cost for the apparatus.
  • the AC discharge type includes, for example, a capacitively coupled type and an inductively coupled type.
  • the gas supply type may, for example, be a nozzle type wherein a nozzle is disposed obliquely to the substrate surface, so that the gas is supplied from one direction, or a shower head type wherein a shower head having a plurality of gas ejection holes is disposed to face against the substrate surface, so that the gas is supplied from the plurality of ejection holes substantially perpendicularly. It is particularly preferred to employ the latter shower head type from the viewpoint of the uniform supply of the gas and the consequent improvement in the utilization efficiency of the gas, and an improvement of the film uniformity.
  • steps (a) and (b) only one condition among the average plasma output per unit time, the atmosphere pressure and the interelectrode distance, is changed.
  • step (b) the average plasma output per unit time
  • step (b) the active species are impinged on the substrate surface at a collision energy relatively lower than in step (a) thereby to carry out film growth.
  • step (a) conditions such as the type of substrate, the type of the gas, the atmosphere pressure, the plasma output, the type of the apparatus, the type of the discharge power source and the interelectrode distance are determined so as to activate the substrate surface to form a sufficient amount of active points and to present no damage other than the surface of the substrate.
  • step (b) plasma irradiation is carried out by relatively lowering the average output per unit time than in step (a).
  • step (a) If the average plasma output (W H ) per unit time in step (a) is too small, active species in an amount to sufficiently activate the substrate surface will not be formed in the plasma, whereby active points will not be formed in a sufficient amount on the substrate surface. Consequently, the amount of a fluorocarbon chemically bonded to the substrate surface tends to be inadequate, and the durability of the fluorocarbon film tends to be inadequate. If the average plasma output (W L ) per unit time in step (b) is too high, the structural regularity of the active species of the monomer tends to be disturbed, whereby it tends to be difficult to form a fluorocarbon having a high structural regularity. Accordingly, the conditions will be decided taking these points into consideration.
  • a substrate having a relatively low heat resistance such as a resin is treated under an atmosphere pressure of from 45 to 55 Pa with an interelectrode distance of from 80 to 100 mm by using hexafluoropropylene oxide as the monomer in step (b) to form CF 2 carbene relatively easily and by using a nozzle type as the gas supply type, a high frequency power source of 13.56 MHz as the discharge power source and a discharge apparatus employing capacitively coupled parallel flat plates, the following conditions are preferred, since a sufficient amount of active points can be formed on the substrate surface, and a fluorocarbon having a high structural regularity at least a part of which is chemically bonded to the substrate, can be constantly obtained.
  • the average plasma output (W H ) per unit time in step (a) is preferably from about 0.1 to 20 W/cm 2 , particularly preferably from about 1 to 10 W/cm 2 .
  • the average plasma output (W L ) per unit time in step (b) is preferably a value relatively lower than in step (a) within a range of from about 0.01 to 5 W/cm 2 , particularly 0.1 to 2.5 W/cm 2 .
  • the ratio in the plasma output per unit time between steps (a) and (b) (W H/ W L ) is preferably at least 1.2, particularly preferably from 2 to 50.
  • step (b) the atmosphere pressure
  • step (b) the active species are permitted to impinge on the substrate surface at a collision energy relatively lower than in step (a) to carry out film growth.
  • the atmosphere pressure is preferably set within a range wherein glow plasma will constantly be generated (no arc plasma will be generated).
  • the atmosphere pressure in steps (a) and (b) is preferably changed within a range of from 10 Pa to atmospheric pressure.
  • the atmosphere pressure in step (a) is preferably from about 10 to 50 Pa, particularly preferably from about 20 to 40 Pa. Further, the atmosphere pressure in step (b) is preferably within a range of from about 30 to 100 Pa, particularly from about 50 to 80 Pa and is a value relatively higher than in step (a).
  • step (b) the interelectrode distance
  • step (a) the active species are permitted to impinge on the substrate surface with a collision energy relatively lower than in step (a) to carry out film growth.
  • the interelectrode distance is preferably set within a range wherein glow plasma will constantly be generated (no arc plasma will be generated).
  • the interelectrode distance in step (a) or (b) is preferably adjusted within a range of from 1 to 300 mm, particularly preferably from 3 to 100 mm.
  • the interelectrode distance in step (a) is preferably from 20 to 60 mm, particularly preferably from 35 to 55 mm.
  • the interelectrode distance in step (b) is preferably from 50 to 100 mm, particularly preferably from 70 to 80 mm and is a value relatively larger than in step (a).
  • step (a) plasma irradiation is carried out under a relatively severe condition to form active points which will be starting points for film growth, on the substrate surface, and then, in step (b), plasma irradiation is carried out under a relatively mild condition in the presence of a gas for a fluorocompound as a monomer to carry out film growth, whereby a fluorocarbon film excellent in the durability and functionality (such as water and oil repellency, anti-fouling property, release property, weather resistance, low refractive index characteristic, low friction property and chemical resistance) can be constantly formed.
  • a fluorocarbon film excellent in the durability and functionality such as water and oil repellency, anti-fouling property, release property, weather resistance, low refractive index characteristic, low friction property and chemical resistance
  • the process for producing a fluorocarbon film of the present invention is simply required to change the plasma irradiation condition such as the average plasma output per unit time, the atmosphere pressure or the interelectrode distance, as between steps (a) and (b). Therefore, as is different from the prior art (2) mentioned in "BACKGROUND ART" wherein it is required to change the gas composition sequentially introduced, the process for producing a fluorocarbon film of the present invention is excellent in the continuous productivity and is far simple in the process.
  • the fluorocarbon film of the present invention is not limited in making the film thin. Namely, it is possible to form a shortest chain fluorocarbon film (theoretically, a film thickness of about 0.3 nm) having a monomolecular layer of CF 3 groups simply bonded to the substrate.
  • the thickness of the fluorocarbon film is not particularly limited. However, in consideration of the merit in making the film thin (such as reduction of the costs) or the stability in forming the film (which leads to the durability or functionality) by the present invention, the thickness is preferably at most 10 ⁇ m, more preferably at most 1 ⁇ m, further preferably at most 0.5 ⁇ m. The film thickness is most preferably within a range of from 0.4 to 100 nm. Here, with a commercially available one having a fluororesin laminated on another substrate, the film thickness is usually more than 10 ⁇ m.
  • the fluorocarbon film of the present invention is characterized in that it is one produced by the above-described process for producing a fluorocarbon film of the present invention.
  • a fluorocarbon film may be formed which has a structural regularity not heretofore attained.
  • the fluorocarbon of the present invention is not substantially branched, and a linear fluorocarbon is formed in a high proportion.
  • a fluorocarbon having a relatively short chain with from about 2 to 8 carbon atoms may be constantly formed. If it is assumed that a linear fluorocarbon having a relatively short chain with from about 2 to 8 carbon atoms is present in a perpendicular direction to the substrate surface, the film thickness at that time will be from about 0.4 to 2 nm.
  • the above phenomenon means that among CF groups, CF 2 groups and CF 3 groups, it is possible to minimize the molar amount of CF groups located at branching points and to increase the molar amount of CF 3 groups located at terminals. Namely, when a fluorocarbon of the same mass is to be formed, according to the present invention, more fluorine atoms may be introduced, and the effects by introduction of fluorine atoms (water and oil repellency, anti-fouling property, release property, weather resistance, low refractive index characteristic, low friction property, chemical resistance, etc.) can be obtained at a higher level.
  • fluorine atoms water and oil repellency, anti-fouling property, release property, weather resistance, low refractive index characteristic, low friction property, chemical resistance, etc.
  • a fluorocarbon film at least a part of which is chemically bonded to a substrate surface and which contains at most 8 mol% of CF group, from 20 to 90 mol% of CF 2 group and from 10 to 80 mol% of CF 3 group, based on the total amount of CF group, CF 2 group and CF 3 group.
  • CF group it is possible to bring CF group to at most 5 mol% or even to 0%, while CF 3 group is maintained at a high level of from 10 to 80 mol%.
  • the amount of CF 3 group is preferably from 13 to 60 mol%, more preferably from 15 to 50 mol%.
  • the relation between the amount of CF 3 group and the amount of CF group is preferably (amount of CF 3 group)>(amount of CF group) ⁇ 2.
  • the amount of CF 3 group is preferably at most 80 mol%.
  • the fluorocarbon film of the present invention can be made to be a thin film having a structural regularity of a high level not attained heretofore and is excellent in the durability and functionality (water and oil repellency, anti-fouling property, release property, weather resistance, low refractive index characteristic, low friction property, chemical resistance, etc.).
  • the fluorocarbon film provided with a substrate of the present invention is characterized in that it is one having the above-described fluorocarbon film of the present invention formed on a substrate surface.
  • the fluorocarbon film provided with a substrate of the present invention is one having the fluorocarbon film of the present invention and thus has the same effects as the fluorocarbon film of the present invention.
  • MCW process the process of the present invention by plasma irradiation in a plurality of steps
  • CW process the process of the present invention which includes a step of carrying out pulse plasma irradiation
  • pulse process a comparative process by continuous plasma irradiation in one step
  • pulse process a comparative process by pulse plasma irradiation in one step
  • the film composition of a formed fluorocarbon film i.e. mol% of CF group, CF 2 group and CF 3 group was obtained by taking a narrow spectrum of the 1s orbit of carbon atoms of the fluorocarbon film by an X-ray photoelectron spectroscopic apparatus (ESCA, Model 5500 manufactured by PHI) and subjecting it to peak division into C, CF, CF 2 and CF 3 .
  • ESA X-ray photoelectron spectroscopic apparatus
  • the contact angle of the formed fluorocarbon film against water was measured by a contact angle measuring apparatus (CA-X150, manufactured by Kyowa Interface Science Co., LTD.).
  • a fluorocarbon film was formed by using a nozzle type as the gas supply type, a high frequency power source of 13.56 MHz as the discharge power source and capacitively coupled parallel flat plates.
  • Fig. 1 shows a schematic construction view of this discharge apparatus.
  • a polyethylene terephthalate (PET) film (substrate 12) (film thickness: 50 ⁇ m) was placed, and the gas in a chamber 1 was evacuated from an exhaust port 7 under reduced pressure until the pressure became not more than 1 Pa. While evacuating under reduced pressure, high purity nitrogen gas was supplied at 110 sccm to replace the interior of the chamber 1 with nitrogen gas. Thereafter, 62 sccm of hexafluoropropylene oxide (HFPO) gas and 5 sccm of high purity nitrogen gas were supplied to bring the atmosphere pressure to be 50 Pa. After the pressure was stabilized, the distance between the upper electrode 2 and the lower electrode 3 i.e. the interelectrode distance was adjusted to be 100 mm.
  • PET polyethylene terephthalate
  • step (a) 2.5 W/cm 2 (W H ) of a high frequency power of 13.56 MHz was applied to the electrodes to generate continuous plasma and maintained for two minutes (step (a)). Thereafter, the high frequency power was continuously reduced at a rate of 0.30 W/cm 2 per minute to a level of 0.13 W/cm 2 (step (b1)). Further, continuous plasma with a power of 0.13 W/cm 2 (W L ) was continuously applied for 20 minutes (step (b2)) to complete the film formation (MCW method).
  • Film forming was carried out in the same manner as in Example 1 except that as shown in Table 1, after adjusting the interelectrode distance to be 100 mm, steps (a) and (b1) were not carried out, and 0.13 W/cm 2 of a high frequency power of 13.56 MHz was applied to the electrodes to generate continuous plasma and maintained for 20 minutes (CW method).
  • (p) represents pulse irradiation.
  • the wide line is the spectrum of the observed value; the dotted line is the spectrum derived from PET; and the narrow line is a spectrum showing the film composition after the peak resolution.
  • Example 1 CF group was 6.7%, and the CF 3 group was 15.4%, and a fluorocarbon film rich in the CF 3 group with a smaller molar amount of CF group, was obtained.
  • the depth analysis by ESCA was carried out, whereby at a depth of 2 nm, only the peak of PET of the substrate appeared, whereby the film thickness was found to be at most 2 nm.
  • the fluorocarbon film in Example 1 had a large contact angle of 120° and good water-repellency. Whereas, a commercially available PTFE film has a contact angle of from about 110 to 115°, and it is evident that the fluorocarbon film in Example 1 has a functionality higher than the commercially available PTFE film.
  • the wiping efficiency of a white board marker after 50 times of the wiping test was also good, and the durability of the film was also good.
  • Such good results are considered to be attributable to the fact that at least a part of the obtained fluorocarbon film is chemically bonded to the substrate surface. This is considered to be supported from the evaluation of the active points (radicals) on the substrate surface in the test example given hereinafter.
  • FIG. 5 shows a schematic construction view of this discharge apparatus.
  • the apparatus in Fig. 5 is the same as the apparatus in Fig. 1 except that the gas supply type was changed to a shower head type (gas ejection holes: 100 holes), and the same components as in the apparatus in Fig. 1 are identified by the same symbols, and their detailed description will be omitted.
  • step (b1) As shown in Table 2, in Examples 2 and 3, there was no step corresponding to step (b1) in Example 1, and step (a) was followed immediately by step (b). Further, the plasma output in steps (a) and (b) was the same, and instead, the gas supply amount was changed to let the atmosphere pressure change from 30 Pa to 70 Pa, so that in step (b), the active species were permitted to impinge on the substrate surface with a collision energy relatively lower than in step (a) to carry out the film forming.
  • Example 2 the same gas (HFPO) was used in steps (a) and (b), while in Example 3, argon (Ar) was used in step (a), and HFPO was used in step (b). On the other hand, in Comparative Example 3, no step (a) was carried out.
  • Film forming was carried out in the same manner as in Example 2 except that the conditions were changed as shown in Table 3.
  • the plasma output in steps (a) and (b) was the same, the gas supply amount was constant at 62 sccm to adjust the atmosphere pressure to be constant at 50 Pa, and instead, the interelectrode distance was changed from 40 to 78 mm, so that in step (b), the active species were permitted to impinge on the substrate surface with a collision energy relatively lower than in step (a), to carry out the film forming.
  • Film forming was carried out in the same manner as in Example 2 except that the number of gas ejection holes of the shower head was changed to 5, and the conditions were changed as shown in Table 4.
  • Example 6 Film forming was carried out in the same manner as in Example 2 except that the conditions were changed as shown in Table 5.
  • the supply gas was a mixed gas of HFP/Ar, and the atmosphere pressure was 10,000 Pa throughout the entire process.
  • HFP represents hexafluoropropylene.
  • step (a) the following test was carried out to confirm that active points are formed on the substrate surface.
  • step (a) in Example 3 plasma irradiation was stopped and nitrogen was introduced into the chamber to the atmospheric pressure. Then, while nitrogen was supplied, the chamber was opened, and the sample was put into a test tube in the chamber, and the test tube was closed in the nitrogen atmosphere. Immediately thereafter, the test tube was cooled with liquid nitrogen, and the amount of remaining radicals was measured by means of ESR measurement (using JES-TE300, manufactured by JEOL DATUM). The mass of the sample was 6.87 mg.
  • the ESR spectrum is shown in Fig. 6.
  • the peak intensity obtained by deducting the blank peak intensity of 8,317 was 4,126, and the peak intensity per unit mass was 601 mg -1 . From this result, it was confirmed that active points (radicals) were formed on the substrate surface after step (a).
  • the fluorocarbon film presented by the present invention is excellent in the durability and at the same time is excellent also in the functionality such as water and oil repellency, anti-fouling property, release property, weather resistance, low refractive index characteristic, low friction property and chemical resistance, and thus, it is preferably used as e.g. various high performance films such as release films.
EP05800431A 2004-11-02 2005-11-01 Film de fluorocarbone et procédé servant à produire celui-ci Withdrawn EP1816231A4 (fr)

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GB2516978A (en) * 2013-08-09 2015-02-11 Innovia Films Ltd Process
WO2018005109A1 (fr) * 2016-06-30 2018-01-04 3M Innovative Properties Company Revêtement antiadhésif à base de fluorocarbone

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US7615501B2 (en) * 2005-08-11 2009-11-10 3M Innovative Properties Company Method for making a thin film layer
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JP6076197B2 (ja) * 2013-05-30 2017-02-08 株式会社吉野工業所 蒸着容器
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JP2016207788A (ja) * 2015-04-20 2016-12-08 東京エレクトロン株式会社 上部電極の表面処理方法、プラズマ処理装置及び上部電極
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GB2516978B (en) * 2013-08-09 2016-06-08 Innovia Films Ltd Process for manufacturing a release liner
GB2534080B (en) * 2013-08-09 2017-05-03 Innovia Films Ltd Manufacturing a release liner
GB2534080A (en) * 2013-08-09 2016-07-13 Innovia Films Ltd Process
WO2018005109A1 (fr) * 2016-06-30 2018-01-04 3M Innovative Properties Company Revêtement antiadhésif à base de fluorocarbone
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EP3478779B1 (fr) * 2016-06-30 2021-10-06 3M Innovative Properties Company Revêtement antiadhésif à base de fluorocarbone

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KR20070102482A (ko) 2007-10-18
TW200624451A (en) 2006-07-16
JP4924038B2 (ja) 2012-04-25
WO2006049153A1 (fr) 2006-05-11
US20070202340A1 (en) 2007-08-30
JPWO2006049153A1 (ja) 2008-05-29
CA2586258A1 (fr) 2006-05-11

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